CN100443522C - Polymerized thylene carbonate urethane elastomer and its preparation method - Google Patents
Polymerized thylene carbonate urethane elastomer and its preparation method Download PDFInfo
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Abstract
The present invention relates to a polymerized thylene carbonate urethane polyurethane elastomer and a preparation method thereof. The elastomer is obtained by reaction of 100 parts by weight of polycarbonate polyatomic alcohol made of carbon dioxide and oxirane, 20 to 60 parts by weight of diisocyanate, 0.05 to 2 parts by weight of polymerization inhibitor, 2.4 to 17 parts by weight of chain extender and /or crosslinking agent, and 0 to 0.4 part by weight of catalyst. The preparation method of the present invention has the advantages of environmental protection and low cost, and the polymerized thylene carbonate urethane polyurethane elastomer which is obtained has the characteristics of fine mechanical performance, plasticity, oxidation resistance, hydrolyzation resistance, and good microbial degradation. The present invention can be used for elastic lining, sieve plates, rubber rollers, sealing rings, shoe soles, polyurethane paving materials, medical instruments, and medical devices which are implanted into a body for a long term.
Description
Technical field
The present invention relates to a kind of aliphatic polycarbonate type polyurethane elastomerics, relate to a kind of polymerized thylene carbonate urethane elastomer specifically, also relate to this method for preparing polyurethane elastic body in addition.
Background technology
Used polycarbonate polyol in aliphatic polycarbonate type polyurethane elastomer production, studying morely both at home and abroad has polymerized thylene carbonate hexylene glycol esterdiol, polymerized thylene carbonate butanediol ester glycol, poly (propylene carbonate) glycol etc.Be that raw material synthesizes the polycarbonate polyurethane elastomerics (Xie Xingyi that a class has good biological property for example with poly-own diamyl glycol carbonate dibasic alcohol, Liu is anti-, clock elecscreen etc. the biomedical engineering magazine, 1999,16 (supplementary issues): 121-122), perhaps synthesize some solvent-proof aliphatic polycarbonate type polyurethane elastomerics (Harris R F, Joseph M D, avidson C D et al.JAppl Polym Sci, 1990,41:487-507), perhaps with poly (propylene carbonate) and tolylene diisocyanate (TDI) be raw material synthesized the poly (propylene carbonate) polyurethane elastomer (Peng Han etc. the synthetic and performance of poly (propylene carbonate) polyurethane elastomer. chemistry world, 1995,8:426-428).
Above-mentioned used polycarbonate polyol mainly is by phosgene interfacial polycondensation, melt transesterification or cyclic carbonate open loop method synthetic, preceding two kinds of methods have all been used phosgene in building-up process, be easy to cause environmental pollution, the cost of ring-opening polymerization method is then too high.Though the multipolymer that the employed polyvalent alcohol of people such as Harris prepares by carbonic acid gas and oxyethane, yet carbonate group mass contg wherein is less, and before with this polyvalent alcohol input reaction, also under comparatively high temps, carried out transesterification reaction with the small molecules polyvalent alcohol, very big change has taken place in the structure of polycarbonate polyol, thereby not only improved cost, and the physicals of the polyurethane elastomer that obtains is not high.
Summary of the invention
The objective of the invention is to develop a kind of polyurethane elastomer with higher physicals, another purpose is to develop the lower-cost preparation method of this polyurethane elastomer.
Polymerization under the catalysis of macromolecule loading double metal cyanide obtains polycarbonate polyol by carbonic acid gas and oxyethane in the present invention, then with the polyvalent alcohol dehydration degassing that obtains, add vulcabond then, can continue to add stopper this moment, chainextender, linking agent, or add catalyzer again and obtain polyurethane elastomer, also pre-polymerization under inhibitor action earlier, add chainextender again, linking agent, or add catalyzer again and obtain polyurethane elastomer, these two kinds of methods are all with low cost, the elastomerics of gained has good physicals, thereby has realized purpose of the present invention.
Polymerized thylene carbonate urethane elastomer of the present invention, obtain by following raw material anabolic reaction: according to the mass fraction, 100 parts of polymerized thylene carbonate dibasic alcohol, 20～60 parts of vulcabond, 0.05～2 part of stopper, 2.4～17 parts of chainextender and/or linking agents, 0～0.4 part of catalyzer, the number average relative molecular mass of described polymerized thylene carbonate dibasic alcohol is between 1000～5000, and hydroxy functionality is 2～4, and carbonate group mass contg wherein is a massfraction 20%～40%.
Described polymerized thylene carbonate dibasic alcohol can promptly be obtained by regulating polymerization under the catalysis of macromolecule loading double metal cyanide by carbonic acid gas and oxyethane with reference to the preparation of the method among the Chinese patent ZL91109459.
Described vulcabond is the cyanate that contains two cyanic acid groups in the molecule, preferably uses the diphenylmethanediisocyanate or the tolylene diisocyanate of carbodiimide modification.
Described stopper is that the preparation polyurethane elastomer is commonly used, can be Tosyl chloride, concentrated hydrochloric acid or phosphoric acid etc.
Described chainextender can be one or more the mixture in micromolecular diamine, the dibasic alcohol, for example 3,3 '-two chloro-4,4 '-ditan diamines, 1, contains one or more the mixture in the above small molecules of two hydroxyls at 4-butyleneglycol, ethylene glycol.
Described linking agent is that the preparation polyurethane elastomer is commonly used, it can be one or more the mixture etc. in micromolecular trivalent alcohol, the tetravalent alcohol, the for example mixture of one or more in TriMethylolPropane(TMP), glycerine, the tetramethylolmethane, preferably TriMethylolPropane(TMP).
Described catalyzer is preparation polyurethane elastomer organic tin metallic compound commonly used, for example dibutyl tin laurate.
The preparation method of polymerized thylene carbonate urethane elastomer of the present invention can adopt general polycarbonate polyurethane method for producing elastomers, be to adopt single stage method or pre-polymerization method, described single stage method comprises the steps: the polymerized thylene carbonate dibasic alcohol dehydration degassing, add vulcabond, stopper and chainextender and/or linking agent, or add catalyzer again, mix, temperature reaction, then the curing cross-linked post curing obtains product; Described pre-polymerization method comprises the steps: the polymerized thylene carbonate dibasic alcohol dehydration degassing is added vulcabond and stopper and carries out pre-polymerization, and then add chainextender, linking agent, or adds catalyzer again, mixes, and the curing cross-linked post curing obtains product.
Used polymerized thylene carbonate dibasic alcohol, vulcabond, stopper, chainextender, linking agent and catalyzer are as previously mentioned.
The pre-polymerization time of described pre-polymerization method is 1～3 hour, 70～75 ℃ of pre-polymerization temperature, 2～4 hours curing cross-linked time, 70～80 ℃ of curing cross-linked temperature, 100～120 ℃ of curing temperatures, 4～8 hours curing times; In the described single stage method, the temperature reaction temperature is 70～75 ℃, and the reaction times is 3～4 hours, and the curing cross-linked time is 2～5 hours, 70～80 ℃ of curing cross-linked temperature, 100～120 ℃ of curing temperatures, 6～8 hours curing times.Mixing described in single stage method and the pre-polymerization method can be adopted conventional powerful paddling process.
Polymerized thylene carbonate urethane elastomer of the present invention (PEC-PUE) is compared with traditional polyvalent alcohol institute synthetic polyurethane material, has mechanical property preferably, plasticity-, oxidation-resistance, therefore hydrolytic resistance and good microbic resolvability have been widely used: can be used for cushions, sieve plate, rubber roll, sealing-ring, sole and urethane pavement material etc.; Because its self-vulcanizing performance is good, can be used as polyurethane coating; Because its good biocompatibility can be used as medicine equipment.This material is a kind of ep-type material in addition, also has purposes widely aspect aqueous environment and the medical treatment device that implants for a long time.Can regulate its hardness, tensile strength and elongation at break according to the different of proportioning raw materials and reaction process, thereby satisfy the service requirements of a relative broad range.Preparation method of the present invention exists even without catalyzer and also can finish, and the polymerized thylene carbonate dibasic alcohol in the raw material utilizes the carbonic acid gas preparation, thereby has saved petroleum resources, has reduced cost.Polymerized thylene carbonate urethane elastomer of the present invention is different from aromatic urethane elastomer, molecular chain is soft, has good room temperature kindliness, the major cause that causes its peculiar property is that synthetic raw materials used polymerized thylene carbonate ethyl ester polyvalent alcohol (PEC) is different from traditional polycarbonate material, and it is close with the how pure and mild polyether polyol of aliphatic polyester, its character and has lower T between aliphatic polyester and polyethers
g
Embodiment
Following examples are to further specify of the present invention, but the invention is not restricted to following examples, used polymerized thylene carbonate dibasic alcohol is promptly obtained by regulating polymerization under the catalysis of macromolecule loading double metal cyanide by carbonic acid gas and oxyethane with reference to the preparation of the method among the Chinese patent ZL91109459.
Embodiment 1:
(the number average relative molecular mass is 1000 to get polymerized thylene carbonate ethyl ester dibasic alcohol, hydroxy functionality is 2, carbonate group mass contg wherein is a massfraction 20%) 100 parts in the there-necked flask of 250mL, adds 2 parts of massfractions and be 36%～38% concentrated hydrochloric acid, at 90 ℃ of dehydration degassing 2h down.Be cooled to 60 ℃, add the diphenylmethanediisocyanate (its NCO massfraction is 29.7%) of 60 parts of carbodiimide modifications, adopt powerful whipping appts (agitator speed 2000r/min), be warming up to 75 ℃ of reaction 1h, vacuum defoamation gets performed polymer.
1,0.86 part of mixed evenly back of 10.4 parts of 4-butyleneglycols (chainextender) and TriMethylolPropane(TMP) (linking agent) adds powerful stirring the in the above performed polymer, pours mould after the vacuum defoamation rapidly into, 80 ℃ of following curing cross-linked 4h, 110 ℃ of following slaking 6h.
The physicals of the product after the measurement demoulding, the result is as follows:
Tensile strength (GB 528-98, same under the testing method): 12.4MPa
Elongation at break (GB 528-98, same under the testing method): 241.8%
Shore A hardness (GB 531-99, same under the testing method): 52 degree.
Embodiment 2:
(the number average relative molecular mass is 5000 to get polymerized thylene carbonate ethyl ester dibasic alcohol, hydroxy functionality is 4, carbonate group mass contg wherein is a massfraction 40%) 100 parts in the there-necked flask of 250mL, adds 2 parts of massfractions and be 36%～38% concentrated hydrochloric acid, at 90 ℃ of dehydration degassing 2h down.Be cooled to 60 ℃, add the diphenylmethanediisocyanate (its NCO massfraction 29.7%) of 24 parts carbodiimide modification, adopt powerful whipping appts (agitator speed 2000r/min), be warming up to 70 ℃ of reaction 3h, vacuum defoamation gets performed polymer.
Get 4.48 parts of TriMethylolPropane(TMP)s that dewatered (linking agent) and add powerful stirring the in the above performed polymer, pour mould after the vacuum defoamation rapidly into, 75 ℃ of following curing cross-linked 2h, 120 ℃ of following slaking 5h.
The physicals of the product after the measurement demoulding, the result is as follows:
Tensile strength: 7.62MPa; Elongation at break: 170.8%; Shore A hardness: 64 degree.
Embodiment 3:
(the number average relative molecular mass is 2000 to get polymerized thylene carbonate ethyl ester dibasic alcohol, hydroxy functionality is 2, carbonate group mass contg wherein is a massfraction 20%) 100 parts in the there-necked flask of 250mL, adds 2 parts of massfraction volumes and be 36%～38% concentrated hydrochloric acid, at 90 ℃ of dehydration degassing 2h down.Be cooled to 60 ℃, add the diphenylmethanediisocyanate (its NCO massfraction 29.7%) of 30 parts of carbodiimide modifications, adopt powerful whipping appts (agitator speed 2000r/min), be warming up to 75 ℃ of reaction 3h, vacuum defoamation gets performed polymer.
Get 5.6 parts dewatered 1,4-butyleneglycol (chainextender) adds powerful stirring the in the above performed polymer, pours mould after the vacuum defoamation rapidly into, 80 ℃ of following curing cross-linked 2h, 100 ℃ of following slaking 8h.
The physicals of the product after the measurement demoulding, the result is as follows:
Tensile strength: 6.07MPa; Elongation at break: 329.2%; Shore A hardness: 54 degree.
Embodiment 4:
Get polymerized thylene carbonate ethyl ester dibasic alcohol (number average relative molecular mass 2000, hydroxy functionality is 2, carbonate group mass contg wherein is a massfraction 20%) 100 parts in the there-necked flask of 250mL, adds 2 parts of massfractions and be 36%～38% concentrated hydrochloric acid, at 90 ℃ of dehydration degassing 2h down.Be cooled to 60 ℃, add the diphenylmethanediisocyanate (its NCO massfraction 29.7%) of 30 parts of carbodiimide modifications, adopt powerful whipping appts (agitator speed 2000r/min), be warming up to 75 ℃ of reaction 2h, vacuum defoamation gets performed polymer.
Get 17 part 3,3 '-two chloro-4,4 '-ditan diamines (MOCA) fusion adds powerful stirring the in the above performed polymer as chainextender, pours mould rapidly into, 70 ℃ of following curing cross-linked 4h, 100 ℃ of following slaking 6h.
The physicals of the product after the measurement demoulding, the result is as follows:
Tensile strength: 14.2MPa; Elongation at break: 69.52%; Shore A hardness: 94 degree.
Embodiment 5:
Get 100 parts of polymerized thylene carbonate ethyl ester dibasic alcohol (number average relative molecular masses 4000, hydroxy functionality is 4, carbonate group mass contg wherein is a massfraction 30%) in the there-necked flask of 250mL, add 2 parts of massfractions and be 36%～38% concentrated hydrochloric acid, at 90 ℃ of dehydration degassing 2h down.Be cooled to 60 ℃, the diphenylmethanediisocyanate (its NCO massfraction 29.7%) that adds 25.8 parts of carbodiimide modifications, the dibutyl tin laurate that adds 0.4 part again, adopt powerful whipping appts (agitator speed 2000r/min), be warming up to 75 ℃ of reaction 1h, vacuum defoamation gets performed polymer.
Get 2.1 parts of glycerine that dewatered, add in the performed polymer and stir, get 4.0 part 3 again, 3 '-two chloro-4,4 '-ditan diamines (MOCA) fusion adds powerful stirring the in the above performed polymer as chainextender, pours mould after the vacuum defoamation rapidly into, 70 ℃ of following curing cross-linked 3h, 120 ℃ of following slaking 4h.
The physicals of the product after the measurement demoulding, the result is as follows:
Tensile strength: 5.46MPa; Elongation at break: 269.6%; Shore A hardness: 42 degree.
Embodiment 6:
Get polymerized thylene carbonate ethyl ester dibasic alcohol (number average relative molecular mass 2000, hydroxy functionality is 2, carbonate group mass contg wherein is a massfraction 25%) 100 parts in the there-necked flask of 250mL, add 0.05 part of Tosyl chloride, at 90 ℃ of degassing 2h that dewater down, add 2.4 parts of TriMethylolPropane(TMP)s that dewatered and mix.
After this polyol blends is cooled to 60 ℃, the diphenylmethanediisocyanate (its NCO massfraction 29.7%) that adds 20 parts of carbodiimide modifications, adopt powerful whipping appts (agitator speed 2000r/min), be warming up to 70 ℃ of reaction 4h, pour mould after the vacuum defoamation rapidly into, 80 ℃ of following curing cross-linked 2h, 120 ℃ of following slaking 6h.
The physicals of the product after the measurement demoulding, the result is as follows:
Tensile strength: 4.85MPa; Elongation at break: 371.8%; Shore A hardness: 22 degree.
Embodiment 7:
Get polymerized thylene carbonate ethyl ester dibasic alcohol (number average relative molecular mass 2000, hydroxy functionality is 2, carbonate group mass contg wherein is a massfraction 25%) 100 parts in the there-necked flask of 250mL, add 0.10 part of phosphoric acid, at 90 ℃ of following dehydration degassing 2h, add 2.0 parts of dewatered tetramethylolmethane and 0.8 part of TriMethylolPropane(TMP) and mix.
After this polyol blends is cooled to 60 ℃, the diphenylmethanediisocyanate (its NCO massfraction 29.7%) that adds 20 parts of carbodiimide modifications, adopt powerful whipping appts (agitator speed 2000r/min), be warming up to 75 ℃ of reaction 3h, pour mould after the vacuum defoamation rapidly into, 70 ℃ of following curing cross-linked 5h, 100 ℃ of following slaking 8h.
The physicals of the product after the measurement demoulding, the result is as follows:
Tensile strength: 5.25MPa; Elongation at break: 271.6%; Shore A hardness: 32 degree.
Embodiment 8:
Get polymerized thylene carbonate ethyl ester dibasic alcohol (number average relative molecular mass 2000, hydroxy functionality is 2, carbonate group mass contg wherein is a massfraction 20%) 100 parts in the there-necked flask of 250mL, adds 2 parts of massfractions and be 36%～38% concentrated hydrochloric acid, at 90 ℃ of dehydration degassing 2h down.Be cooled to 60 ℃, add 45 parts tolylene diisocyanate, adopt powerful whipping appts (agitator speed 2000r/min), be warming up to 70 ℃ of reaction 3h, vacuum defoamation gets performed polymer.
1,10.4 parts of 4-butyleneglycols and 3,3 '-two chloro-4,3.2 parts of (chainextender) mixed evenly backs of 4 '-ditan diamines add powerful stirring the in the above performed polymer, pour mould after the vacuum defoamation rapidly into, 80 ℃ of following curing cross-linked 2h, 100 ℃ of following slaking 8h
The physicals of the product after the measurement demoulding, the result is as follows:
Tensile strength: 13.6MPa; Elongation at break: 169.2%; Shore A hardness: 56 degree.
Claims (7)
1. polymerized thylene carbonate urethane elastomer, its raw material is composed as follows: according to the mass fraction, 100 parts of polymerized thylene carbonate ethyl ester dibasic alcohol, 20～60 parts of vulcabond, 0.05～2 part of stopper, 2.4～17 parts of chainextender and/or linking agents, 0～0.4 part of catalyzer, the number average relative molecular mass of described polymerized thylene carbonate ethyl ester dibasic alcohol is between 1000～5000, and hydroxy functionality is 2～4, and carbonate group mass contg wherein is a massfraction 20%～40%; And prepare: adopt single stage method or pre-polymerization method by following method, described single stage method comprises the steps: the polymerized thylene carbonate ethyl ester dibasic alcohol dehydration degassing, add vulcabond, stopper, chainextender, linking agent, or add catalyzer again, mix, temperature reaction, then the curing cross-linked post curing obtains product; Described pre-polymerization method comprises the steps: the polymerized thylene carbonate ethyl ester dibasic alcohol dehydration degassing, add vulcabond and stopper and carry out pre-polymerization, and then add chainextender, linking agent, or add catalyzer again, mix, the curing cross-linked post curing obtains product.
2. according to a kind of polymerized thylene carbonate urethane elastomer of claim 1, wherein said vulcabond is the cyanate that contains two cyanic acid groups in the molecule, described stopper is a Tosyl chloride, concentrated hydrochloric acid, boron trifluoride diethyl etherate or phosphoric acid, described chainextender is 3,3 '-two chloro-4,4 '-ditan diamines, 1, the 4-butyleneglycol, one or more mixture in the ethylene glycol, described linking agent is a TriMethylolPropane(TMP), glycerine, the mixture of one or more in the tetramethylolmethane, described catalyzer are the organic tin metallic compounds.
3. according to a kind of polymerized thylene carbonate urethane elastomer of claim 1 or 2, wherein said vulcabond is the diphenylmethanediisocyanate of tolylene diisocyanate or carbodiimide modification, and described catalyzer is a dibutyl tin laurate.
4. the preparation method of the polymerized thylene carbonate urethane elastomer of claim 1, adopt single stage method or pre-polymerization method, described single stage method comprises the steps: the polymerized thylene carbonate ethyl ester dibasic alcohol dehydration degassing, add vulcabond, stopper, chainextender, linking agent, or add catalyzer again, mix, temperature reaction, then the curing cross-linked post curing obtains product; Described pre-polymerization method comprises the steps: the polymerized thylene carbonate ethyl ester dibasic alcohol dehydration degassing, add vulcabond and stopper and carry out pre-polymerization, and then add chainextender, linking agent, or add catalyzer again, mix, the curing cross-linked post curing obtains product.
5. according to the preparation method of a kind of polymerized thylene carbonate urethane elastomer of claim 4, wherein said vulcabond is the cyanate that contains two cyanic acid groups in the molecule, described stopper is a Tosyl chloride, concentrated hydrochloric acid or phosphoric acid, described chainextender is 3,3 '-two chloro-4,4 '-ditan diamines, 1, the 4-butyleneglycol, the mixture of one or more in the ethylene glycol, described linking agent is a TriMethylolPropane(TMP), glycerine, the mixture of one or more in the tetramethylolmethane, described catalyzer are the organic tin metallic compounds.
6. according to the preparation method of a kind of polymerized thylene carbonate urethane elastomer of claim 4 or 5, wherein said vulcabond is the diphenylmethanediisocyanate of tolylene diisocyanate or carbodiimide modification, and described catalyzer is a dibutyl tin laurate.
7. according to the preparation method of a kind of polymerized thylene carbonate urethane elastomer of claim 4 or 5, the pre-polymerization time of wherein said pre-polymerization method is 1～3 hour, 70～75 ℃ of pre-polymerization temperature, 2～4 hours curing cross-linked time, 70～80 ℃ of curing cross-linked temperature, 100～120 ℃ of curing temperatures, 4～8 hours curing times; The temperature reaction temperature is 70～75 ℃ in the described single stage method, and the reaction times is 3～4 hours, and the curing cross-linked time is 2～5 hours, 70～80 ℃ of curing cross-linked temperature, 100～120 ℃ of curing temperatures, 6～8 hours curing times.
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